The invention relates to a lubricating composition which is particularly appropriate for lubricating curing bladders used during the shaping and curing of pneumatic or semipneumatic tires.
The invention also relates to the curing bladders coated with a lubricating composition according to the invention as well as the pneumatic or semipneumatic tires coated with said lubricating composition.
According to two other of its aspects, the invention relates to a process for preparing the lubricating compositions of the invention as well as the use of said lubricating compositions for lubricating curing bladders.
Rubber tires for vehicles are usually manufactured by molding and curing a raw, or uncured and unshaped, envelope in a molding press in which the raw envelope is pressed toward the outside against the surface of a mold by means of a bladder which can expand by means of an inner fluid. By this process, the raw envelope is shaped against the outer surface of the mold which defines the design of the tire tread of the envelope and the configuration of t sides. On heating, the envelope ""s cured. In general, the bladder is expanded by the inner pressure provided by a fluid such as a hot gas, hot water and/or steam, which itself also participates in the heat transfer for the curing. The envelope is then allowed to cool a little in the mold, this cooling being sometimes promoted by the introduction of cold or cooler water into the bladder. The mold is then opened, the bladder is deflated by releasing the pressure of the inner fluid and the envelope is removed from the envelope mold. This use of bladders for curing envelopes is well known in the art.
It is accepted that a notable relative movement occurs between the outer surface of contact of the bladder and the inner surface of the envelope during the bladder expansion phase before complete curing of the envelope. Likewise, a considerable relative movement also occurs between the outer surface of contact of the bladder and the cured inner surface of the envelope, after the envelope has been molded and cured, during the deflation and the extraction of the bladder from the pneumatic tire.
If adequate lubrication is not provided between the bladder and the inner surface of the envelope, the bladder generally tends to get warped, which causes deformation of the envelope in the mold and also excessive wear and depolishing of the surface of the bladder itself. The surface of the bladder also tends to stick to the inner surface of the envelope after curing of the envelope and during the part of the envelope curing cycle in which the bladder is deflated. In addition, air bubbles may be trapped between the surfaces of the bladder and of the envelope and may promote the appearance of envelope curing defects resulting from inadequate heat transfer.
For this reason, the outer surface of the bladder or the inner surface of the raw or uncured envelope is coated with an appropriate lubricant, sometimes called by the name xe2x80x9clining cementxe2x80x9d.
Numerous lubricating compositions have been provided to this effect in the art.
Lubricating compositions described in FR 2 494 294 are known in particular which contain, as main constituents, a reactive polydimethylsiloxane preferably having terminal hydroxyl groups, a crosslinking agent, preferably comprising Sixe2x80x94H functional groups and optionally a polycondensation catalyst.
Examples of crosslinking agent with Sixe2x80x94H functional group(s) are methylhydrogensilane, dimethylhydrogensilane and polymethylhydrogenslane. The disadvantage of lubricating compositions of this type is their instability during storage. Indeed, creaming of the emulsion following the emission of hydrogen during transport and the preservation of the lubricating composition is observed. The emission of hydrogen, which is responsible for the instability of the compositions of the prior art, essentially results from the decomposition of the constituents with Sixe2x80x94H functional group(s).
The preparation of lubricating compositions from constituents not containing the Sixe2x80x94H functional group, and having nevertheless excellent properties of durability, lubrication and elasticity is therefore highly desirable.
The compositions forming the subject of EP 635 559 are lubricating compositions based on siloxane which partly meet these requirements. These compositions are in particular stable in that they do not emit hydrogen during storage.
These compositions, which exist in the form of emulsions, comprise as essential constituents, a nonreactive polydimethylsiloxane, a reactive polydimethylsiloxane, preferably with a hydroxyl or alkoxy terminus and a crosslinking agent. Their durability is however insufficient for practical use in the production of pneumatic or semipneumatic tires.
The present invention provides an improved lubricating composition which does not emit hydrogen and which moreover exhibits excellent sliding and durability characteristics, which makes them perfectly appropriate for lubricating the bladders used during the curing of pneumatic and semipneumatic tires.
The lubricating composition of the invention is an oil-in-water emulsion, based on siloxane which does not emit hydrogen. This composition comprises more precisely:
(a) a polydiorganosiloxane oil which is nonreactive to the lubricating properties, having a dynamic viscosity of the order of 5xc3x9710xe2x88x922 to 30xc3x97102 Pa.s at 25xc2x0 C.;
(b) a polyorganosiloxane resin carrying, before emulsification, condensable hydroxyl substituents and containing, before emulsification, at least two different siloxyl units chosen from those of formula (R0)3SiO1/2(M); (R0)2SiO2/2(D); R0SiO3/2(T) and SiO4/2(O), at least one of these units being a T or Q unit, in which formulae R0 represents a monovalent organic substituent, the average number per molecule of organic radicals R0 for a silicon atom being between 1 and 2; and said resin having a weight content of hydroxyl substituents of between 0.1 and 10% by weight, and, preferably between 0.2 and 5% by weight;
(c) a crosslinking agent which is soluble in the silicone phase, comprising at least two functional groups capable of reacting with the polyorganosiloxane resin (b);
(d) a condensation catalyst capable of catalyzing the reaction of constituent (b) with constituent (c);
(e) a surfactant; and
(f) water,
said composition comprising
from 5 to 95 parts by weight of constituent (a);
from 0.5 to 50 parts by weight of constituent (b);
from 0.1 to 20 parts by weight of constituent (c);
from 0.05 to 10 parts by weight of constituent (d);
per 100 parts by weight of the sum of constituents (a)+(b)+(c)+(d);
the quantities of surfactants and water being sufficient to obtain an oil-in-water emulsion.
The constituents (a), (b), (c), (d) and (e) of the emulsion are defined with reference to their initial chemical structure, that is to say the structure which characterizes them before emulsification. As soon as they are in aqueous medium, their structure is likely to be greatly modified following hydrolysis and condensation reactions.
The expression dynamic viscosity is understood to mean, in the context of the invention, the Newtonian-type viscosity, that is to say the dynamic viscosity measured in a manner known per se at given temperature, at a gradient of shear rate which is sufficiently low for the measured viscosity to be independent of the rate gradient.
The nonreactive polydiorganosiloxane oil (a) has a dynamic viscosity which is generally between 5xc3x9710xe2x88x922 and 30xc3x97102 Pa.s at 25xc2x0 C. Preferably, the dynamic viscosity varies between 5xc3x97102 and 30 Pa.s, better still between 0.1 and 5 Pa.s.
In the context of the invention, the expression xe2x80x9cnonreactivexe2x80x9d is understood to mean an oil which, under the conditions for emulsification, preparation of the lubricating composition and use, does not chemically react with any of the components of the composition.
As preferred constituent (a), there may be mentioned linear polydiorganosiloxanes with a recurring unit of formula V1V2SiO2/2, terminated at its chain ends by V3V4V5SiO1/2 units, V1, V2, V3, V4 and V5, which are identical or different, representing a monovalent organic group chosen from alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, aralkyl or alkaryl.
In these oils, alkyl denotes a linear or branched saturated hydrocarbon group, preferably a C1-C6 (such as methyl, ethyl and propyl); alkenyl denotes a linear or branched ethylenicallyu unsaturated hydrocarbon group, preferably a C2-C8 (such as vinyl, allyl and butadienyl); aryl denotes a hydrocarbon-based mono- or polycyclic aromatic group, preferably as C6-C10 (such as phenyl or naphthyl); cycloalkyl denotes a mono- or polycyclic saturated carbocyclic group, preferably as C3-C8 (such as cyclohexyl); cycloalkenyl denotes a cycloalkyl group having one or more unsaturations, preferably as C6-C8 (such as cyclohexenyl); aralkyl denotes for example benzyl; alkaryl denotes for example tolyl or xylyl. More generally, alkaryl and aralkyl denote groups in which the aryl and alkyl portions are as defined above.
Advantageously, the substituents V1, V2, V3, V4 and V5 are identical to each other.
Preferably, the constituent (a) is a linear, nonfunctionalized polydimethylsiloxane, that is to say with recurring units of formula (CH3)2SiO2/2 and having (CH3)3SiO12 units at its two ends.
The constituent (a) is generally introduced into the composition in an amount of 5 to 95 parts by weight per 100 parts by weight of the mixture of constituents (a)+(b)+(c)+(d), preferably in an amount of from 50 to 95, better still in an amount of 75 to 95.
The constituent (b) is a polyorganosiloxane resin carrying, before emulsification, condensable hydroxyl groups.
In the constituent units of these resins, each substituent R0 rep-resents a monovalent organic group.
In general, R0 is a C1-C20 hydrocarbon radical optionally carrying one or more substituents.
Examples of hydrocarbon radicals are a linear or branched saturated or unsaturated, aliphatic group preferably having from 1 to 10 carbon atoms; a saturated, unsaturated or aromatic, monocyclic or polycyclic, carbocyclic group preferably having from 3 to 18 carbon atoms, better still from 5 to 10 carbon atoms; or a radical having an aliphatic part as defined above and a carbocyclic part as defined above.
The substituents of the hydrocarbon radical may be xe2x80x94ORxe2x80x2 or xe2x80x94Oxe2x80x94COxe2x80x94Rxe2x80x2 groups in which Rxe2x80x2 is an unsubstituted hydrocarbon radical as defined above.
Other substituents of the hydrocarbon radical may be groups containing amines, amides, epoxides or a ureido functional group.
By way of example of substituents of the hydrocarbon radical, there may be included amine-containing functional groups of the type:
xe2x80x94Raxe2x80x94NR1R2 in which
Ra represents nothing or represents a saturated or unsaturated, linear or branched divalent C1-C20, preferably C1-C10, aliphatic hydrocarbon radical, and for example (C1-C10)alkylene;
and R1 and R2 independently represent H; a (C1-C20)alkyl, preferably (C1-C10)alkyl, group; a (C3-C8)cycloalkyl group; or a (C6-C10)aryl, preferably phenyl, group;
xe2x80x94Rbxe2x80x94NHxe2x80x94Rcxe2x80x94NR1R2 in which Rb and Rc, which are identical or different, are as defined for Ra above; and R1 and R2 are as defined above; 
in which R3 represents C1-C20 alkyl, better still (C1-C10)alkyl, for example (C1-C3)alkyl and in particular methyl; (C6-C20) aryl, better still (C6-C10)aryl, for example phenyl; or arylalkyl in which the aryl and alkyl portions are as defined above;
R4 represents a hydrogen atom; C1-C20 alkyl, better still (C1-C12)alkyl, for example methyl; C2-C21 alkylcarbonyl, better still (C2-C13)alkylcarbonyl; (C6-C20) aryl, better still (C6-C10)aryl, for example phenyl; or arylalkyl and preferably (C6-C10)aryl-(C1-C12)alkyl; or alternatively R4 represents O; and 
in which R3 and R4 are as defined above.
Arylalkyl is preferably benzyl.
It is however preferable that the concentration of xe2x80x94ORxe2x80x2, xe2x80x94Oxe2x80x94COxe2x80x94Rxe2x80x2, amine, amide, epoxide or ureido groups, when they are present in the resin, is limited so as not to exceed the tolerance threshold above which the stability of the emulsion would be compromised.
The silicone resins (b) are well known branched organopolysiloxane polymers whose methods of preparation are described in numerous patents. As concrete examples of resins which can be used, there may be mentioned the hydroxylated resins MQ, MDQ, DQ, ST and MDT and mixtures thereof. In these resins, each OH group is carried by a silicon atom belonging to an X, D or T unit.
Preferably, as examples of resins which can be used, there may be mentioned the hydroxylated organopolysiloxane resins not comprising a Q unit in their structure. More preferably, there may be mentioned the hydroxylated resins DT and MDT comprising at least 20% by weight of T units and having a weight content of hydroxyl group ranging from 0.1 to 10%, and even better from 0.2 to 5%. In this group of more preferred resins, those in which the average number of substituents R0 for a silicon atom is, per molecule, between 1.2 and 1.8, are more particularly suitable. Still more advantageously, resins of this type are used, in whose structure at least 80% in numerical terms of the substituents R0 are methyl radicals.
The resin (b) is liquid at room temperature. Preferably, the resin has a dynamic viscosity at 25xc2x0 C. of between 0.2 and 200 Pa.s.
The resin is incorporated into the lubricating composition in an amount of from 0.5 to 50 parts by weight per hundred parts by weight of the sum of the constituents (a), (b), (c) and (d), preferably in an amount of 3 to 30, even better from 5 to 15 parts by weight.
The crosslinking agent (c) which is soluble in the silicone phase comprises at least two functional groups capable of reacting with the resin (b) so as to cause crosslinking of said resin. Advantageously, said reactive functional groups of the crosslinking agent (c) react with the resin (b) under the conditions for preparing the emulsion.
The crosslinking agent (c) preferably has the formula:
YaSi(Zi)4-a 
in which:
a is 1 or 2;
Y is a monovalent organic group; and
the groups Zi, which are identical or different, are chosen from xe2x80x94OX.; 
and xe2x80x94Oxe2x80x94Nxe2x95x90CX1X2 in which Xa, Xb, X1 and X2 are independently saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals, preferably a Cxe2x80x94, xe2x80x94C20 (for example a C1-C10); it being understood that X1 and X2 may in addition represent hydrogen and that Xa is a radical optionally substituted with (C1-C10)alkoxy.
According to a preferred embodiment of the invention, a represents 1, such that the crosslinking agent (c) has the formula: YSi(Zi)3.
Preferably still, the Zi groups are identical to each other.
A preferred group of crosslinking agent (c) is formed by all the organotrialkoxysilanes, organotriacyloxysilanes, organotrioximosilanes and tetraalkyl silicates.
More generally, as regards the symbol Y, the expression xe2x80x9cmonovalent organic groupxe2x80x9d encompasses in particular saturated or unsaturated, linear or branched C1-C30 aliphatic radicals; saturated, unsaturated or aromatic, mono- or polycyclic C6-C30 carbocyclic radicals; as well as radicals having both an aliphatic portion as defined above and a carbocyclic portion as defined above; each s: these radicals being optionally substituted with an amino, epoxy, thiol or ester functional group.
Examples of groups Y are more particularly the (C1-C10)alkyl, (C1-C10)alkoxy or (C2-C10)alkenyl radicals, optionally substituted with a group:
epoxy;
thiol;
(C3-C8)cycloalkyl optionally substituted with epoxy;
(C1-C10)alkylcarbonyloxy optionally substituted with epoxy;
(C2-C10)alkenylcarbonyloxy optionally substituted with epoxy;
(C3-C8)cycloalkylcarbonyloxy optionally substituted with epoxy;
(C6-C10)arylcarbonyloxy;
xe2x80x94Raxe2x80x94NR1R2 where Ra, R1 and R2 are as defined above;
xe2x80x94Rbxe2x80x94NHxe2x80x94Rcxe2x80x94NR1R2 where Ra, Rb, R1 and R2 are as defined above; 
xe2x80x83in which R3 and R4 are as defined above; 
xe2x80x83It is preferable that R3 represents methyl, phenyl or benzyl and R4 represents H or methyl.
Still more preferably, Y is unsubstituted (C2-C10)alkenyl; or alternatively (C1-C10)alkyl optionally substituted with a group chosen from:
thiol;
(C1-C10)alkylcarbonyloxy optionally substituted with epoxy;
(C3-C8)cycloalkyl optionally substituted with epoxy;
(C2-C10)alkenylcarbonyloxy; and
xe2x80x94Raxe2x80x94NR1R2 where Ra represents nothing or represents (C1-C6)alkylene and R1, R2 independently represent H, (C3-C8)cycloalkyl or (C6-C10)aryl and in particular phenyl.
By way of example, Y represents aminopropyl, ethylaminopropyl, n-butylaminoethyl, cyclohexylamino-propyl, phenylaminoethyl, N-aminoethylaminopropyl, dimethylaminopropyl, glycidyloxypropyl, 3,4-epoxycyclo-hexylethyl, mercaptopropyl, methacryloxypropyl, methyl, ethyl or vinyl.
The groups Zi are advantageously chosen from (C1-C10)alkoxy; (C1-C10)alkoxy-(C1-C10)alkoxy; (C1-C10)alkylcarbonyloxy; or an ox-me group xe2x80x94Oxe2x80x94Nxe2x95x90CX1X2 in which X1 and X2 are independently H or (C1-C10)alkyl.
Preferably, Zi represents methoxy, ethoxy, propoxy, methoxyethoxy, acetoxy or an oxime group.
A particularly preferred group of constituents (c) is formed by alkyltrialkoxysilanes of formula YSi(Zi)3 in which Y is alkyl, in particular (C1-C30)alkyl (preferably (C1-C10)alkyl) and Zi is alkoxy, in particular (C1-C20) alkoxy, preferably (C1-C10) alkoxy.
Among these, there may be mentioned methyltrimethoxysilane and methyltriethoxysilane.
Other appropriate crosslinking agents (c) are described in U.S. Pat. No. 4,889,770, such as:
beta-aminoethyltrimethoxysilane,
beta-aminoethyltriethoxysilane,
beta-aminoethyltriisopropoxysilane,
gamma-aminopropyltrimethoxysilane,
gamma-aminopropyltriethoxysilane
gamma-aminopropyltri(n-propoxy) silane,
gamma-aminopropyl(n-butoxy)silane,
delta-aminobutyltrimethoxysilane,
epsilon-aminohexyltriethoxysilane,
4-aminocyclohexyltriethoxysilane,
A-aminophenyltrimethoxysilane,
N-aminoethyl-gamma-aminopropyltrimethoxysilane,
N-aminoethyl-gamma-aminopropyltriethoxysilane,
beta-glycidoxyethyltrimethoxysilane,
beta-glycidoxyethyltriethoxysilane,
gamma-glycidoxypropyltriethoxysilane,
beta-(3,4-epoxycyclohexyl)ethyltrimethoxy-silane,
beta-(3,3-epoxycyclohexyl)ethyltriethoxy-silane,
gamma-(3,4-epoxycyclohexyl)propyltriethoxy-silane,
gamma-mercaptopropyltrimethoxysilane,
gamma-mercaptopropyltriethoxysilane,
gamma-methacryloxypropyltrimethoxysilane,
gamma-methacryloxypropyltriethoxysilane,
methyltrimethoxysilane,
ethyltriethoxysilane,
vinyltrimethoxysilane,
allyltrimethoxysilane,
and the corresponding compounds in which the alkoxy groups have been replaced by alkylcarbonyloxy or oxime groups.
The lubricating composition comprises from 0.1 to 20 parts by weight, per one hundred parts by weight of the sum of the constituents (a)+(b)+(c)+(d), of the crosslinking agent (c), Preferably from 0.2 to 10 parts by weight, even better from 0.5 to 5.
The condensation catalyst (d) is chosen from those conventionally used in the art to catalyze the crosslinking of resins of the (b) type using crosslinking agents of the (c) type which are defined above.
Examples of catalysts which can be used in the context of the invention are organometallic salts, and titanates such as tetrabutyl orthotitanate. As organometallic salt, there may be mentioned zirconium naphthenate and zirconium octylate.
Said catalyst is preferably a tin-containing catalytic compound, generally an organotin salt.
The organotin salts which can be used are described in particular in the manual by NOLL, Chemistry and Technology of Silicones, Academic Press (1968), page 337. It is also possible to define as tin-containing catalytic compound either distannoxanes, or polyorganostannoxanes, or the product of the reaction of a tin salt, in particular of a tin dicarboxylate, with polyethyl silicate, as described in patent U.S. Pat. No. 3,862,919.
The product of the reaction of an alkyl silicate or of an alkyltrialkoxysilane with dibutyltin diacetate as described in Belgian patent BE 842 305, may also be suitable.
According to another possibility, a tin II salt, such as SnCl2 or stannous octoate, is used.
Advantageously, the catalyst is the tin salt of an organic acid, such as dibutyltin diacetate, dibutyltin dilaurate, dioctytin dilaurate, dibutyltin dioctate, zinc naphthenate, cobalt naphthenate, zinc octylate, cobalt octylate and dioctyltin di(iso-mercaptoacetate).
The preferred tin salts are tin bischelates (EP 147 323 and EP 235 049), diorganotin dicarboxylates and, in particular, dibutyl- or dioctyltin diversatates (British patent GB 1 289 900, dibutyl- or dioctyltin diacetate, dibutyl- or dioctyltin dilaurate or the products of hydrolysis of the precipitated species (for example diorgano and polystannoxanes).
The catalyst (d) is generally introduced into the lubricating composition in an amount of 0.05 to 10 parts by weight, per one hundred parts by weight of the sum of the constituents (a)+(b)+(c)+(d) preferably in an amount of 0.08 to 5 parts by weight, and better still from 0.1 to 2 parts by weight.
Dioctyltin dilaurate is most particularly preferred.
The nature of surfactant (e) will be easily determined by persons skilled in the art, the objective being to prepare a stable emulsion.
The anionic, cationic, nonionic and zwitterionic surfactants may be used alone or as a mixture.
As anionic surfactant, there may be mentioned the alkali metal salts of sulfonic aromatic hydrocarbon-containing acids or the alkali metal salts of alkylsulfuric acids.
The nonionic surfactants are more particularly preferred in the context of the invention. Among them, there may be mentioned alkyl or aryl ethers of poly(alkylene oxide), polyoxyethylenated sorbitan hexastearate, polyoxyethylenated sorbitan oleate having a saponification value of 102 to 108 and a hydroxyl value of 25 to 35 and the ethers of cetylstearyl and of poly(ethylene oxide).
As acrylic ether of poly(alkylene oxide), there may be mentioned polyoxyethylenated alkylphenols. As alkyl ether of poly(alkylene oxide), there may be mentioned isodecyl ether of polyethylene glycol and trimethylnonyl ether of polyethylene glycol containing from 3 to 15 ethylene oxide units per molecule.
The quantity of surfactant (e) depends on the type of each of the constituents present as well as on the actual nature of the surfactant used. As a general rule, the composition comprises from 0.5 to 10% by weight of surfactant (better still from 0.5 to 5% by weight) and from 40 to 95% by weight of water (better still from 45 to 90% by weight).
Advantageously, the lubricating composition of the invention may comprise, in addition, a water-soluble crosslinklng agent (g) chosen from hydroxylated silanes and/or polydiorganosiloxanes, said crosslinking agent carrying, per molecule, at least one organic group with an Fr functional group, Fr representing an optionally substituted amino functional group, an epoxy, optionally substituted acroyl (CH2xe2x95x90CHxe2x80x94CO), optionally substituted methacroyl (xe2x80x94CH2xe2x95x90C(CH3)xe2x80x94COxe2x80x94), optionally substituted ureido (NH2xe2x80x94COxe2x80x94NHxe2x80x94), optionally substituted thiol or halogen functional group.
For the purposes of the present invention, the expression water solubility should be understood to mean the capacity of a product to dissolve in water at a temperature of 25xc2x0 C., in an amount of at least 5% by weight.
The organic substituents of the crosslinking agent (g) other than the organic group(s) with an Fr functional group are saturated or unsaturated, linear or branched, aliphatic radicals preferably having from 1 to 10 carbon atoms; saturated, unsaturated or aromatic, monocyclic or polycyclic, carbocyclic radicals preferably having from 3 to 18 carbon atoms, better still from 5 to 10 carbon atoms; or radicals having both an aliphatic portion and a carbocyclic portion.
According to a preferred embodiment of the invention, Fr is an amine-containing functional group.
Thus, a preferred organic group with an Fr functional group is a group of formula xe2x80x94Raxe2x80x94NR1R2; xe2x80x94Rbxe2x80x94NHxe2x80x94Rcxe2x80x94NR1R2; 
and 
where Ra, Rb, Rc, R1, R2, R3 and R4 are as defined above.
According to a preferred embodiment of the invention, the water-soluble crosslinking agent has the formula:
R2R1Nxe2x80x94Raxe2x80x94Si(OH)3 
in which Ra, R1 and R2 are as defined above. More preferably, Ra represents alkylene, in particular (C1-C6)alkylene, and R1 and R2 independently represent a hydrogen atom or an alkyl, in particular (C1-C6)alkyl, group.
By way of example, 3-aminopropyltrihydroxy-silane may be mentioned.
The water-soluble crosslinking agent may be a linear and/or cyclic hydroxylated polydiorganosiloxane containing MD and/or D siloxyl units, and/or a hydroxylated polydiorganosiloxane resin having, in its structure, siloxyl units T optionally combined with units M and/or D and/or Q, or alternatively siloxyl units Q combined with M and/or D units.
This linear, cyclic or crosslinked polydiorganosiloxane is not substituted with hydrolyzable organic functional groups such as alkoxy functional groups.
In these polydiorganosiloxanes, the siloxyl units M, D, T and Q are defined as follows:
M, unit=G3SiO1/2 
D unit=G2SiO1/2 
T unit=GSiO3/2 
Q unit=SiO4/2, 
G being an organic substituent as defined above for the crosslinking agent (g), or alternatively representing hydroxyl or alternatively being an For functional group, it being understood that in each molecular structure, at least one of the symbols G represents a hydroxyl group and at least another of the symbols G represents an Fr functional group.
Preferably, G is alkyl, in particular (C1-C6)-alkyl (for example methyl, ethyl, isopropyl, tert-butyl and n-hexyl), hydroxyl, alkenyl (for example vinyl or allyl) or alternatively an Fr functional group, the preferred Fr functional groups being as defined above.
As linear hydroxylated polydiorganosiloxane which can be used as crosslinking agent (g), there may be mentioned polymethylsiloxane the two ends of which contain a hydroxyl and therefore each silicon atom of the chain carries an Fr functional group.
This constituent (g), when it is present in the lubricating composition, is used in an amount of 0.5 to 15 parts by weight per one hundred parts by weight of the sum or the constituents (a)+(b)+(c)+(d)+(g), preferably in an amount of 0.6 to 5 parts by weight, and even better from 0.8 to 3 parts by weight.
The presence of the crosslinking agent (g) improves in particular the durability of the lubricating composition.
In addition, the composition of the invention may further comprise (h) a reactive linear polydiorganosiloxane oil having at least two OH groups per molecule, having a dynamic viscosity at 25xc2x0 C. generally of between 5xc3x9710xe2x88x922 and 30xc3x97102 Pa.s.
In the context of the invention, the term xe2x80x9creactivexe2x80x9d denotes the reactivity of the constituent (h) toward the crosslinking agents (c) and/or (g) present in the composition.
Preferably, the component (h) reacts with the crosslinking agent under the conditions for preparing the emulsion.
The organic substituents of the oil (h) are generally as defined above in the case of the crosslinklng agent (g) (aliphatic and/or carbocyclic groups) and are optionally substituted with xe2x80x94OH and/or amino (optionally substituted) and/or halogen and/or cyano radicals. The substituent of the amino group may be an aliphatic radical, a carbocyclic radical, or may comprise both an aliphatic portion and a carbocyclic portion, the aliphatic and carbocyclic radicals being as defined above.
As halogen, here may be mentioned chlorine, fluorine, bromine or iodine, fluorine being more specifically appropriate.
Advantageously, the organic groups of the oil (h) are preferably C1-C6 alkyl groups; preferably C3-C8 cycloalkyl groups, preferably C6-C10 aryl groups (for example phenyl); or C2-C6 alkenyl groups (for example allyl or vinyl); said groups being optionally substituted with hydroxyl and/or amino (optionally substituted), and/or halo, and/or cyano.
The substituents of the amino group are, for example, alkyl, such as (C1-C10)alkyl; alkenyl, such as (C2-C8)alkenyl; aryl, such as (C6-C10)aryl; cycloalkyl, such as (C3-C8)cycloalkyl.
A preferred group of components (h) consists of the oils of formula: 
in which n is an integer greater than or equal to 10, R1 and R2, which are identical or different, represent xe2x80x94OH; alkyl, in particular (C1-C6)alkyl; cycloalkyl, in particular (C3-C8)cycloalkyl; alkenyl, in particular (C2-C6)alkenyl; cycloalkenyl, in particular (C5-C8)cycloalkenyl; or amino.
Preferably, R1 and R2 are independently chosen from (C1-C6) alkyl (such as methyl); (C6-C10)aryl, and for example phenyl; (C2-C8) alkenyl (such as vinyl) or alternatively amino; (C1-C6)alkylamino; or di(C1-C6)-alkylamino; each of the alkyl and aryl groups being optionally substituted with halo (and preferably fluoro) or cyano.
The oils (h) most widely used, because of their availability in industrial products, are those for which R1 and R2 are independently chosen from methyl, ethyl, propyl, phenyl, vinyl and 3,3,3-tri-fluoropropyl. Preferably, 80% in numerical terms of these radicals are methyl radicals.
In practice, xcex1,xcfx89-dihydroxypolydimethyl-siloxanes carrying (CH3)2(OH)SiO1/2 units at the ends will be preferred as oil (h).
In the context of the present invention, there may be especially used the the xcex1,xcfx89-dihydroxy-polydiorganosiloxanes prepared by the anionic polymerization method described in the above-mentioned American patents: U.S. Pat. No. 2,891,920 and especially U.S. Pat. No. 3,294,725 (cited as reference).
The constituent (h), when it is present, is used in an amount from 0.5 to 30% by weight, and preferably from 1 to 10% by weight, relative to the total weight of the composition.
The lubricating composition according to the present invention may also contain one or more additional ingredients such as film-forming polymers, additional lubricants and anti-friction agents, coalescing agents, wetting or dispersing agents, air evacuating agents, antifoaming agents, thickeners, stabilizers, preservatives such as biocides, antifungal agents in quantities which may vary considerably, for example, between 0.2 and 50% by weight of the composition.
By way of film-forming agent, styrene-acrylic copolymers may be mentioned for example.
Examples of thickeners are cellulosic thickeners (carboxymethylcellulose), acrylic thickeners, polyurethane, hydrocolloidal gums (xanthan gum) and mixtures thereof.
As coalescing agent, glycols and/or aliphatic petroleum cuts (petroleum distillation fractions) may be used.
Wetting or dispersing agents which can be used in the context of the invention are, for example, phosphates and/or polyacrylics, such as for example sodium hexametaphosphate and sodium polyacrylates.
The compositions of the invention may be prepared in a conventional manner using conventional state of the art methods.
A first method consists in emulsifying, in an aqueous phase comprising all the water-soluble constituents, a mixture of the lipophilic constituents (a), (b), (c), (d) and optionally (h), in the presence of the surfactant (e).
Modifications to method can naturally be envisaged. An oil-in-water preemulsion may first of all be prepared from only a few of the constituents forming the final composition. The missing constituents may then be added, either directly to the emulsion (the case for water-soluble constituents), or subsequently in the form of an emulsion (the case for constituents soluble in the silicone phase).
Thus, the catalyst (d), the film-forming polymer and the reactive oil (h) may be added, either directly to the silicone phase before emulsification or after formation of the preemulsion, in the form of an additional emulsion.
The emulsification may be direct or may proceed by inversion.
In the case where the procedure is by inversion, it may be advantageous to prepare a preemulsion containing only a small proportion of water, to carry out its inversion (for example by grinding), and then dilute the resulting emulsion with the remaining water, optionally supplemented with one or more water-soluble constituents.
A preferred variant consists in particular in preparing an oil-in-water preemulsion comprising all the constituents (a), (b) and (c) and optionally (g) in the presence of the surfacant (e) before adding to this preemulsion the missing constituents in the form of additional emulsion(s)
Thus, according to another of its aspects, the invention relates to a method for preparing a lubricating composition according to the invention, comprising the steps consisting in:
xcex1xe2x80x94emulsifying in water (f), a mixture of nonreactive polydiorganosiloxane oil (a), polyorganosiloxane resin (b), and crosslinking agent which is soluble in the silicone phase (c), in the presence or the surfactant (e) so as to prepare an oil-in-water type emulsion;
xcex2xe2x80x94adding to the preceding emulsion, an emulsion of the catalyst (d) in water.
Normally, the method of the invention is carried out at room temperature.
The emulsification, in step xcex1, may be direct or may proceed by inversion. The procedure is preferably carried out by inversion.
When a water-soluble crosslinking agent (g) is incorporated into the lubricating composition, it is preferably incorporated, in the form of an aqueous solution, at the end of step xcex2, into an oil-in-water preemulsion containing all the constituents (a), (b), (c) and (e).
When a reactive linear polydiorganosiloxane oil (h) is present, it is preferably added to the oil-in-water emulsion at the end of step in the form of an oil-in-water preemulsion.
The additional emulsion of the catalyst (d) as well as any emulsion added to the preemulslon resulting from step (a) is preferably prepared in the presence of the same surfactant as step xcex1. However, it is possible to envisage the use of any other type of surfactant, such as for example a poly(vinyl alcohol). The latter surfactant is most particularly useful in the case where it is desired to prepare an additional emulsion of a tin-based catalyst.
The method of the invention may comprise, in addition, an additional step of heating the resulting emulsion. This step makes it possible to accelerate the crosslinking processes. It can be replaced by a step of storing the emulsion at room temperature until complete crosslinking is obtained.
The lubricating properties of the composition of the invention are markedly enhanced in the event of complete crosslinking of the crosslinkable constituents of the composition.
The oils and resins (a), (b) and (h) as well as the crosslinking agents (c) and (g) are commercially available or are easily accessible to a person skilled in the art using conventional methods described in the prior art.
When the resin (b) or the crosslinking agent (c) are functionalized, the functionalization is easily carried out by appropriate substitution or addition reaction.
When the optional constituent (g) represents a hydroxylated water-soluble silicone resin, the latter may be obtained:
by cohydrolysis:
of at least one silane (S1) substituted with Fr functional groups or with Hydrolyzable Organic Functional Substituents (Sofh) which are mutually identical or different, preferably xe2x80x94ORd with Rd=hydro-carbon, advantageously alkyl, radical;
with at least one silane (S2) substituted with Sofh substituents which are identical or different with respect to each other and relative to those of (S1), excluding Fr substituents;
by heterocondensation of the hydrolysates derived from the S, and S2 silanes;
and then by xe2x80x9cstrippingxe2x80x9d or steam distillation of the hydrolysates derived from the Sofh substituents.
For the purposes of the invention, the hydrolyzable organofunctional substituents (Sofh), which are capable of generating in situ volatile organic compounds (VOC) during crosslinking by condensation, are for example alkoxy, acetoxy, cetiminoxy and enoxy substituents.
Since the most common Sofh substituents are alkoxyls xe2x80x94ORd, the mechanisms of heterocondensation involved are of the OH/OH and OH-/OFT type, these OH or ORd being carried by the hydrolysates derived from the silanes S1 and S2. The hydrolysates derived from the Sofh substituents are, for their part, alcohols, in this instance.
Thus, in practice, the silane S1 is advantageously a trialkoxysilane, preferably a trimethoxysilane, a triethoxysilane, a methyldimethoxy-silane or a methyldiethoxysilane, carrying an amine-containing functional group Fr of the type:
3-aminopropyl;
N-methyl-3-aminopropyl;
N-aminoethyl-3-aminopropyl;
C6H5CH2NH(CH2)2NHxe2x80x94(CH2)3xe2x80x94;
3-ureidopropyl;
3-(4,5-dihydroimidazol-1-yl)propyl;
3-methacryloxypropyl: CH2xe2x95x90C(CH3)xe2x80x94COOxe2x80x94(CH2)3xe2x80x94;
3-glycidyloxypropyl: 
xe2x80x83(the other substituents of Si in the crosslinking agent (g) being in this case free of Sofh)
3-mercaptopropyl;
3-chloropropyl.
As regards S2, the Sofh substituents which it comprises are preferably advantageously C1-C6 alkoxy radicals, for example: methoxy, ethoxy or propoxy.
This silane S2, preferably an alkoxysilane, may also contain at least one advantageously C1-C6 alkyl substituent, for example: methyl, ethyl, propyl.
These resins, which are produced by heterocondensation of S1 and S2, are described in particular in European patent application No. 0 675 128, whose content is integrated by reference into the present disclosure.
According to a second embodiment, the optional crosslinking agent (g) is a resin obtained:
by hydrolysis of a silane S3 substituted with Fr groups and Sofh substituents,
by homocondensation of the hydrolyzed silanes S3,
and by xe2x80x9cstrippingxe2x80x9d or steam distillation of the hydrolysates derived from Sofh substituents.
The silane S3 is preferably an Fr substituted alkoxysilane. It may be for example a trialkoxysilane which makes it possible to obtain a hydroxylated resin with T units, also called T(OH) resin.
This S3 silane may be of the same type as the S1 silane as defined above. The Fr functional groups substituting S3 correspond to the same definition as that given above.
As illustration of this second embodiment of a crosslinking agent (g) of the polydiorganosiloxane resin type, there may be mentioned that obtained from xcex3-aminopropyltriethoxysilane which is hydrolyzed and subjected to xe2x80x9cstrippingxe2x80x9d of the ethanol Formed by the hydrolysis. The polyhomocondensed resin obtained is a mixture of oligomers containing from 4 to 10 silicone and comprising units:
T(OH)=Rxe2x80x3Si(OH)O2/2 
T=Rxe2x80x3SiO3/2 
T(OH)2xe2x95x90Rxe2x80x3Si(OH)2O1/2 
T(OH)3xe2x95x90Rxe2x80x3Si(OH)3,
these units being respectively present in decreasing quantity, with Rxe2x80x3=NH2xe2x80x94(CH2)xe2x80x943. It is for example an amine-containing resin T(OH).
According to a variant of the invention, the temperature may be increased up to 40xc2x0 C. so as to accelerate the crosslinking of the constituents present.
The present invention also relates to the articles lubricated using the lubricating composition of the invention as well as the use of the lubricating composition of the invention for lubricating various articles.
More particularly, the invention relates to:
an expandable rubber bladder coated on its outer surface with a composition according to the invention, for shaping and curing pneumatic or semipneumatic tires;
an expandable rubber bladder which can be obtained by heating the expandable bladder defined above, in particular at 80-150xc2x0 C. (preferably 100-150xc2x0 C.) so as to ensure complete crosslinklng of the crosslinkable constituents of the emulsion;
a raw pneumatic or semipneumatic tire comprising elements which will constitute its outer tire tread intended to come into contact with the ground, coated on its inner surface with a composition according to the invention;
the use of a lubricating composition according to the invention during the shaping and curing of pneumatic or semipneumatic tires, for the lubrication of the expandable rubber curing bladder.
The lubricating composition of the invention may be applied in any manner, and for example by spraying, brushing or alternatively using a sponge or a brush. It is preferable to carry out the operation so as to cover the article to be coated with a regular layer of coating.
The lubrication of the curing bladder used during the curing of pneumatic or semipneumatic tires may be carried out in two different ways.
During the manufacture of pneumatic or semipneumatic tires, a raw tire is placed in a tire mold, an expandable bladder is placed in the mold, the mold is closed and the bladder is expanded by applying an inner pressure of hot fluid, such that the tire becomes flattened against the mold, shaped and cured. The mold is then opened, the bladder is deflated and the tire is recovered, shaped and cured. The same bladder is used for the manufacture of about a thousand tires.
The expandable rubber bladder used during the manufacture of the tires is initially coated with a composition according to the invention.
At the start, the lubrication of the bladder is direct. Next, the lubricating effect of this bladder is depleted.
In this subsequent phase, it is the inner surface of the tire (that which comes into contact with the bladder) which is coated with the lubricating composition. There is regeneration of the lubrication of the rubber bladder by transfer from the tire.
In general, the mold pressing/bladder release cycles used during the manufacture of the tires are in the following succession:
the bladder, initially coated with the lubricating composition (direct lubrication) and heated at 80-150xc2x0 C. is used without subsequent coating for 5 to 10 cycles (each cycle resulting in the manufacture of a different tire), and then
the next cycles are carried out using this same bladder (for which the lubrication coating has been depleted) starting with pneumatic or semipneumatic tires each time coated with the lubricating composition of the invention: the lubrication of the bladder occurs in this case by transfer.
The lubricating composition of the invention comprises no constituent with an Sixe2x80x94H bond, such that the risk of emission of hydrogen during storage or transport is zero.
The lubricating composition of the invention has, in addition, excellent sliding and durability properties.
The following examples which illustrate the invention demonstrate the excellent lubricating properties of the compositions of the invention.